Resins from high boiling hydrocarbons and asphalts containing the same

ABSTRACT

An aromatic oil say from catalytic cracking of hydrocarbon oil and/or a paraffinic oil as from solvent deasphalting of topped crude is air blown at elevated temperature and then further treated at elevated temperature in the presence of a catalyst, e.g., zinc chloride, to produce a hydrocarbon resin. The oil in which the resin has been produced is combined with a topped crude from which asphalt is to be produced or with an asphalt following which the admixture thus obtained is subjected to vacuum distillation or to a solvent deasphalting to remove unreacted or non-resinous, petroleum-derived fractions. An asphalt suitable for paving, having improved ductility and other properties, is obtained.

United States Patent [1 1 Pitchford et al.

[ 1 RESINS FROM HIGH BOILING HYDROCARBONS AND ASPHALTS CONTAINING THESAME [751 Inventors: Armin C. Pitchford; Gene N.

Woodruff, both of Bartlesville. Okla.

[73] Assignee: Phillips Petroleum Company.

Bartlesville. Okla.

[22] Filed: Sept. I7, 1973 [El] Appl. No: 398.083

{52] US. Cl. 208/4; 208/6; 208/23: 208/39; 208/44; 208/45 [5 l] Int. Cl.C07C 3/08 [58] Field of Search 208/4. 6. 23. 39. 44. 45

{56] References Cited UNITED STATES PATENTS 2.|7 .988 ll/l939 Whit-acre208. 4

2.627.498 2/l953 Fink et al 208M 3.687.989 3/1954 Goodnin 208/62.691.62l 1(l/l954 Gngle 208/13 2.773.004 lZ/l956 Martin 208. 45

[ 1 Nov. 11, 1975 1.774.714 |Z1l95tv Watson 30356 2.904.494 911959Griffin 308. 13 3.3381? 8/1967 \';|n Pool.... 208. 6 3.4401174 {H969Stcrn et al.. 318, 23

3.402.359 W196) Fztuher 118123 3.628.975 I 33197] Vun Pool ZtJtH-l-lPrimary E.\'umiuw'\"eronica OKeefe [57] ABSTRACT An uromutic oil so fromcatalytic cracking of h vdrocarbon oil and/or at puraffinic oil as fromsolvent dealsphalting of topped crude is air blown at elevated temperature and then further treated at elevated temperature in thepresence of a catalyst. e.g.. zinc chloride. to produce a h ulrocarbonresin. The oil in which the resin has been produced is combined with a1topped crude from which asphalt is to be produced or with an usphultfollowing which the admixture thus obtained is subjected to vacuumdistillation or to a solvent dens phulting to remove unreacted orHOII'FLSIHOUS. petroleunrderived fractions. An asphalt suitable forpuving. having improved cluctilit and other properties. is obtained.

[0 Claims. N0 Drawings RESINS FROM HIGH BOILING HYDRQCARBQNS ANDASPHALTS CONTAINING TT-IE SAME This invention relates to the productionof an improved asphalt composition. More particularly it relates to theproduction of an asphaltic resin containing asphalt composition and tothe production of such a resin from an oil, e.g., a waxy crude oil, asdistinguished from a petroleum residuum or asphalt. In one of itsaspects, the invention can produce a final product containing in anasphalt, obtained upon vacuum reduction or a solvent extraction, adesired improved or increased amount or proportion of resinous materialas distinguished from asphaltenes. In another of its aspects, theinvention relates to the production of resinous materials from apetroleum oil, e.g., an oil derived from a synthetic crude oil obtainedby catalytic cracking a virgin gas oil, a solvent gas oil, a heavyresidual oil, a whole crude oil, and similar feedstocks.

The terms employed herein, e.g., oil," resin, petroleum residuum," etc.,have generally accepted meanings in the petroleum refining art and areemployed to convey said meanings.

During the refining of certain crude oils an excess of a particulardistillate or residual fraction may be produced while a shortage ofanother component will occur. Frequently this component can be of valuein the preparation of a refined product for some specific application.Therefore, it is advantageous to convert a less desirable fraction ofthe crude oil to the most useful product without altering the overallcrude charged to the refinery. Thus a change in refinery operation ismade.

An example of this situation exists when a waxy crude oil is used toproduce a distillate fuel and an asphaltic residue containing adeficiency of asphaltic resins. Asphaltic resins are necessary to impartcertain characteristics to the asphalt and to overcome the adverseeffects of the excess wax, which remains in the asphalt phase aftervacuum flash distillation or solvent deasphalting of the oil, as withpropane or with a mixed solvent, e.g., propane and butanes.

In one of its concepts, this invention provides a two stage process forpreparing a resin-containing additive for improving the quality ofasphalts, e.g., as derived from a waxy crude oil, which involves (1) airblowing of an aromatic oil or a heavy vacuum gas oil and (2)subsequently treating the airblown product with'a catalyst, say, zincchloride, at an elevated temperature such that there is formed in theoil a substantial proportion of resin.

In another of its concepts, the invention provides a process in which aresin-containing fraction or resin is added to an asphalt, or to atopped crude from which asphalt is to be prepared, to increase the resincontent of the asphalt without substantially increasing the asphaltenecontent of the resulting blend, which comprises adding a resin orresin-containing fraction or petroleum resin to a topped crude andsubjecting the admixture to a vacuum distillation thus to prepare apaving grade asphalt. In a further concept of the invention, theadmixture is solvent deasphalted to obtain such a grade of asphalt. Inthe operation just described the resin remains in the asphalt to improveconsiderably its properties, e.g., ductility, etc.

It is known in the art to air-blow petroleum residuum at about 300-500"Ffor, say, about 600 minutes and to 2 then subject the air-blownmaterial, thus obtained, to a polymerization treatment as by heating itin the presence of aluminum chloride at 300400F for 20 to 30 minutes.

We have conceived that an oil, as distinguished from a petroleumresiduum, for example a bottoms obtained from a synthetic crude oilobtained by catalytically cracking a virgin gas oil or a solvent gasoil, as obtained from a topped crude by a propane-butane extraction, canbe converted to a resin or resin-containing material or additive whichthen can be incorporated into a topped crude, as herein described, fromwhich asphalt is to be prepared, and the admixture thus obtainedprocessed to produce paving grade asphalt by a vacuum distillation or asolvent deasphalting to remove unreacted oil or gas oil therefrom, theproduct thus obtained being resin-enriched and possessing due to thepresence therein of the added resin, considerably improved ductility andother properties.

An object of this invention is to prepare a petroleum resin. Anotherobject of this invention is to prepare an improved asphalt derived frompetroleum. A still further object of this invention is to prepare aresin to be incorporated into an asphalt, thus to obtain a productsuitable for paving use, and other uses, without however increasingasphaltenes content. A still further object of the invention is toincorporate a petroleum resin, prepared according to the invention, intoa topped crude from which an asphalt is to be prepared or into anasphalt. Another object of the invention is to produce an asphalt ofimproved properties from an oil low in resin content.

Other aspects, concepts, object and the several advantages of theinvention are apparent from a study of this disclosure and the appendedclaims.

According to the present invention, an oil such as herein described isheated and air blown and still later while at an elevated temperature isfurther heated in presence of a catalyst which will produce resinousmaterials in the air-blown material, while avoiding the formation ofasphaltenes, say, ZnCl,, FeCl, and SnCl,, as distinguished from CuCl,and SnCl to produce a resin or resin-containing material suitable forincorporation into a topped crude to be converted to asphalt, say, apaving grade quality. Also according to the present invention, apetroleum derived resin as herein described, as it may be contained inan oil in which produced, is incorporated into an oil to be converted toan asphalt which comprises admixing said material and said oil, e.g.,topped crude or a solvent gas oil and then producing an asphalt in knownmanner, obtaining an asphalt of, say, paving quality, having propertiesconsiderably better than otherwise obtained to date in the art from suchtopped crudes and such solvent gas oils.

Generally, the resin-containing material will improve to an extent theproperties of the final asphalt even when added in small proportions ofthe order of about five percent or even less. However, for now desirablein uses there will be incorporated into the topped crude or asphalt, orthe like, from about I percent up to equal proportions or even more ofthe resin-containing material depending upon the natures of thematerials to be admixed and further treated. Thus, one skilled in theart in possession of this disclosure having studied the same willunderstand that for each oil, treated according to the invention, andfor each set of conditions of treatment, there will be a certainproportion of beneficial resin contained therein and therefore this willhave 3 to be taken into account in admixing the treated oil containingthe resin with the topped crude or asphalt to be benefited.

Thus according to the present invention, in one of its broad concepts, apetroleum fraction or oil is treated to produce a petroleum derivedresin containing oil or oily material which is then admixed with atopped crude or asphalt, or equivalent material, from which by vacuumreduction or solvent extraction a final asphalt is obtained, as hereindescribed.

The invention will now be described further with respect to theapplication of feedstocks, used for the preparation of the syntheticasphalt resins or resin-containing material, as given in Table I.

Table I 4 are properties of the resulting air-blown product andproperties after the second stage catalytic treatment.

The data in the foregoing Table are for purposes of illustration only.Such data will vary from time to time in the normal refining of crudeoil at any particular refinery. At such times, as one skilled in the artin possession of this disclosure having studied the same willunderstand, the conditions of the treatment of the feeds will beadjusted to obtain the results desired. Clearly, properties of oils willvary substantially with crude oil source, operating conditions, and theextent to which a particular oil has been fractionated prior to thereactions which are involved in the production of the resincontainingoil of the present invention.

PROPERTIES OF FEEDSTOCKS USED IN THE PREPARATION OF SYNTHETIC ASPHALTRESINS Syn Tower Rottorns' Solvent Gas Oil Identification A B C D APIGravity at 60 F 6.8 13.6 3.8 23.2 Specific Gravity, 60/60 F 10231 0.97521.0458 0.9147 Viscosity. SFS, 122 F 27.0 47.6 52.2 Viscosity. SUS, 180 F177.6 Viscosity, SUS. 210 F 105.8 Pentane Insolubles, Wt k 1 1.8 5.9Carbon Residue. Rams., Wt l: 7.86 0.78 Elemental Analyses. Wt k Carbon89.2 88.47

Hydrogen 8.7 11.25

Oxygen 0.14

Nitrogen 0.09 0.14

Sulfur 1.42 0.77 Metals, ppm

Nickel 0.7

Vanadium 0.3

Iron 2 Distillation, ASTM D 1160 IBP, "F 577 564 564 780 2 k 616 571 655805 S k 703 680 724 853 I: 839 B47 859 985 Distillation Residue Per Centof Feed 50 50 50 61.8

Viscosity, SFS, 210 F 13.1 7.5 31.4 18.4

Bottoms 01 a fractionator from the catalytic cracking unit.

To demonstrate the operability of the proposed pro- 5 cess the sample ofsyntower bottoms designated as Sample A in the above tabulation wasfirst air blown at conditions presented in Table I]. Included in TableII Table II PREPARATION AND PROPERTIES OF ASPHALTIC RESINS PREPARED FROMSYN TOWER BO'ITOMS First Stage Second Stage Feedstock Air BlowingCatalytic Treatment Run Number A F G H .1 Material Charged A F F BlendCatalyst Used none ZnCI, ZnCl, ZnCI, Wt :1: Catalyst none 1.0 1.0 Gasused in test Air NaLGas NaLGas Gas Rate, SCFH 2.0 1 l Temperature, F 492540 565 Reaction Time, Hours 3.5 6.0 7.0 API Gravity at F 13.6 8.3 6.85.9 6.7 Specific Gravity, 60/60 F 0.9752 1.0122 1.0231 1.0298 1.0239ASTM D 1160 Distillation IBP. F 564 705 725 730 50% 847 871 880 880 879Distillation Residue Per cent of Feed 50 50.8 56.2 55.2 49.3

Table ll-continued PREPARATION AND PROPERTIES OF ASPI-IALTIC RESINSPREPARED FROM SYN TOWER BOTTOMS First Stage Second Stage Feedstock AirBlowing Catalytic Treatment Viscosity, SFS. 2l0 F 7.5 68.7 I666 123.5I49.8

The blend was comprised of about 6! wt it: G and 39 wt I; of productI-I. Calculated viscosity from G and .1 assuming a straight linefunction.

The preceding data indicate that air blowing of the Syntower bottomsproduces a material which, upon distillation, yields a high boilingresidue which is considerably more viscous than the correspondingfraction obtained from the untreated syntower bottoms. Further treatmentof the airblown product with zinc chloride at about 550 F yields an 880F+ residue having a much higher viscosity than resulting from airtreatment alone. Maximum viscosity increase is obtained when ZnCl, isused to treat the air blown intermediate while FeCl and SnCl were eacheffective to a slightly lesser extent. Neither CuCl nor SnCl wereeffective in the second stage treatment. These data are reported inTable III.

measuring the viscosity of the distillation residue. Higher viscositiesas compared to those of a control containing no catalyst indicate a morereactive catalyst. Based upon viscosity data neither CuCl .2H,O nor SnCl.5l-I,O were considered effective as second stage catalysts as comparedto anhydrous ZnCl or to FeCl .6I-I,O. Note also that ZnCl .2H O was notas effective as the anhydrous zinc chloride.

Similar laboratory tests were made to determine the feasibility of usingsolvent gas oil, produced on the solvent deasphalting unit, as afeedstock for the preparation of asphaltic resins. This feed wasconsidered since the amount of resins which can be prepared from a syn-Table III EFFECT OF VARIOUS SECOND-STAGE CATALYSTS FOR INCREASING THEVISCOSITY OF THE 880 F+ DISTILLATION RESIDUE DERIVED FROM AIR BLOWNSYNTOWER BOTTOMS 1st Stage Feed- Air Blowing Second Stage, CatalyticTreatment stock Control I 2 3 4 6 Catalyst. Wt 0 L0 L0 1.0 L0 1.0 1.0Catalyst None None FeCl;.6H,O FeCI,.6I- I,O ZnCl, SnCl .2I-I,OCuCl,.2H,O SnCl .SI-l,O Composition Reaction Temp., F 550 600 540 550550 550 Reaction Time Hours 5.75 6.0 6.0 6.5 6.0 6.0 880 F+ DistillationResidue. Wt 50 50.8 50.0 5L2 56.2 48.7 53.4 52.8 Viscosity of B80 F+Residue, SFS at 2l0 F 7.5 68.7 105.4 I08.7 l66.6 82.9 48.0 36.2

Note: In these tests. the initial oil was feedstock A of Table II.

In these tests, syntower bottoms (air blown at 492 F tower bottom alonemay not meet the demands for asfor 3.5 hours in the first stage of theprocess) were 45 phalt production. Mixtures of resins derived from thetreated at 550 F with 1.0 weight percent catalyst for 5.75 to 6 hours.After this treatment the liquid product was vacuum distilled to yield an880 F+ bottoms product. Effectiveness of the catalyst was determined byseveral procedures can be used to produce the final asphalts. Processingdetails and properties of the airblown intermediate and the ZnCl,treated materials are given in Table IV and Table V.

Table IV PREPARATION AND PROPERTIES OF ASPHALTIC RESINS PREPARED FROMSOLVENT GAS OILS Feedstock. Second Stage Solvent First Stage CatalyticGas Oil Air Blowing Treatment Identification D Catalyst Used NONE ZnCl,Wt. Catalyst NONE 1.0 Gas Used in Test O, steam CH. Gas Rate. SCFH 2.0 IReaction Temperature. "F SIS 560 Reaction Time. Hours 5.5 6.75 APIGravity. 60'F 23.2 19.7 Specific Gravity, 60/60 F 0.9147 0.9358Distillation, ASTM D 1 I60 IBP" F 780 886 2 k 805 923 5 b 853 945 10 l:877 949 i: 913 it 949 k 972 b 985 Distillation Residue Per cent ofProduct 6L8 86.8" 88.6

Table IV-continued PREPARATION AND PROPERTIES OF ASPHALTIC RESINSPREPARED FROM SOLVENT GAS OILS PREPARATION AND PROPERTIES OF ASPHALTICRESINS FROM SOLVENT GAS OIL Feedstock Second Stage Solvent First Stage,Catalytic Gas Oil Air Blowing Treatment Identification D" Catalyst UsedNONE ZnCl, Wt. Catalyst NONE 1.0 Gas Used in Test Air CH Gas Rate, SCFH2.0 1 Reaction Temperature. F 550-575 560 Reaction Time. Hours 70 6.0API Gravity, 60 F 23.2 19.4 17.1 Specific Gravity. 60/60 "F 09147 0.93770.9522 Distillation, ASTM D 1 160 lBP F 780 874 901 2 it 805 901 945 5it 853 937 972 lb 877 960 913 k 949 972 50 k 985 Distillation ResiduePer cent of Product 87.6 94.4 Viscosity, SFS at 210 F 50.5 81.0

Table l Attention is directed to Table V, showing a substanthe secondstage catalytic treatment (81 SFS) as compared to the original feedstock(18.4 SFS) and the air blown intermediate (50.5 SFS). Higher viscosity(81.0 SFS) of the distillation residue is obtained upon ZnCl, catalytictreatment when the gas oil is subjected to more severe air blowing(Table V) prior to the second stage catalytic treatment as compared tothe less severe air blowing of Table IV (viscosity of 35.9 SFS).

The material obtained as the distillation residue after Additional testshave been made to determine 5 whether a combination of syntower bottomsand solvent gas oil could be used as a feedstock for the production ofsynthetic resins. While the reaction mechanism is not known, it isbelieved that the more aromatic components of the feedstocks arepossibly alkylated in the presence of ZnCl, with the more paraffinicmaterials. Therefore, a mixture of air blown syntower bottoms, which aremore aromatic, and air blown solvent gas oil which is paraffinic, shouldresult in a highly resinous material with properties substantiallydifferent the two-stage treatment in Table V having a viscosity of fromthose of corresponding products obtained from 81 SF S was very tacky andresembled the resins separated from paving asphalts by other methods.

each of the separate feedstocks. Preparation and some properties of theresins from the mixed air blown feedstocks are shown in Table VI.

Table VI Feedstock First Stage Air Blowi Syntower Solvent SyntowerSolvent Second Stage Charge Bottoms Gas Oil Bottoms Gas Oil CatalyticIdentification B" D Blend Catalyst Used NONE NONE NONE NONE ZnCl, Wt.Catalyst NONE NONE NONE NONE 1 Gas Used Air Air CH. Gas Rate. SCFH 2.02.0 1.0 Reaction Temperature, "F 375 530 560 Reaction Time, Hours 2.56.0 5.5 API Gravity, 60 F 13.6 23.2 13.7 Specific Gravity, 60/60 F0.9752 0.9147 0.9745 Distillation, ASTM D 1160 18? "F 564 780 693 2 I:571 805 743 5 k 680 853 780 I0 '1: 730 877 817 20 i: 768 913 853 30 i;802 949 889 40 I: 819 972 935 847 985 Distillation Residue Per cent ofProduct 50 61.8 56.0

Table VI-continued Feedstock First Stage Air Blowing Syntower SolventSyntower Solvent Second Stage Charge Bottoms Gas Oil Bottoms Gas OilCatalytic Viscosity, SFS at 2l0 F 7.5 1 8 .4 72.2

Blend consisted of 47.4 wt. 1: air blown syntower bottoms and 52.3 wt.K: blown solvent gas oil.

While the actual viscosity of the distillation residue of the blend ofair blown syntower bottoms and air blown solvent gas oil followed bysecond stage catalytic treatment was 72.2 SFS at 210F., the material wastacky and resembled resins separated from paving asphalts by variousmethods.

These results confirm that resinous materials are formed by thepreceding sequence of reactions. However, the viscosity increase in thisexample is believed to be minimum and is expected to increase with anincrease in the severity of the air blowing at higher temperatures ofthe syntower bottoms. Feedstocks that can be used in this invention arethose containing a substantial amount of aromatics, i.e., at least aboutpercent aromatics to obtain ordinarily economically feasible results.That is, sufficient aromatics must be available to form reasonablequantities of resin in the oil subjected to the two-stage treatment ofthe invention; syntower bottoms, light and heavy cycle oils, phenolextract oils, SO, extract oil, vacuum and solvent extract oils. 7

Properties of feedstocks which are suitable for the preparation ofsynthetic resins for use as asphalt additives are given in Table VII.

Table VI! PROPERTIES OF FEEDS'IOCKS SUITABLE FOR THE PREPARATION OFSYNTHETIC RESINS FOR USE AS ASPHALT ADDITIVES Range of Prgerties Thetemperature for air blowing may range from about 350 to about 600 F.,preferably 400 to 550 F.

The temperature of the catalytic treatment may range from about 500 F toabout 600 F, preferably 530 to 570 F.

The selected temperature, in any case, whether within or outside theGwen ranges can be determined by test.

When compared with corresponding asphaltic materials obtained from thesame feedstock containing none of the added synthetic resins, asphaltsprepared in the manner disclosed in this invention have improved qualityas determined by viscosity, ductility and other tem- Jperature dependentcharacteristics.

While the asphalt prepared in accordance with this invention can beprepared in a number of different ways, the following method illustratesthe process and shows the improvement in the properties of the finalasphaltic product containing the synthetic resins.

Ordinarily, the amount of resin-containing oil from the second stage orcatalytic treatment added to a topped crude or to an asphalt will be inthe range of from about 1/ l0 to about 10 weight percent, or more,depending upon the properties of the resin, and, of course, of the finalasphalt desired to be obtained.

It is possible within the scope of the appended claims to first treatthe second stage catalytically treated, resin-containing oil to removethe oil therefrom, as by solvent deoiling, and to recover resin and tothen add the thus concentrated resin to an asphalt cement to improve itsproperties. In such instance, the proportion of resin added can besmaller understandably because with oil has been largely, if notcompletely, removed from the resin.

The a prioritreatment to concentrate the resin is not now preferredbecause this involves additional steps and equipment. Obviously, theaddition of the resin containing oil to a topped crude, which is to be avacuum distilled and/or solvent deasphalted, is more attractive from aneconomic viewpoint.

In the following Table VIII product .I of Table II, obtained by thesuccessive dual stage treatment of syntower" bottoms with air and thenwith ZnCl, at temperatures ranging from 250 to about 600 F, was added toa 430 F+ topped crude representing the current total charge to therefinery. The mixture thus obtained contained 4 wt. percent of thesynthetic resin fraction. It was further distilled to yield a 650 F+bottoms which was subsequently charged to a semi-continuous isothermalvacuum flash distillation unit to yield various grades of asphaltcements for use in highway paving applications. These asphaltscontaining the synthetic resins are compared to similar materials, inthe following tabulations, derived from the same 430 F+ topped crude butwhich contained no additive. Solvent extraction can be employed witheven greater success, to yield asphalts of improved quality from the 650F+ topped crude.

According to the invention, the synthetic resins can be concentrated byeither vacuum reduction or by solvent extraction and then added toasphalt previously produced by some other means. It is within the scopeof the invention to at least partly effect a concentration of the resinscontaining product, to then admix it with a topped crude or asphalt andto then produce the final asphaltic product as herein described. Ineither instance more resinous portion of the reaction product wouldremain in the final asphaltic residue.

Table V111 EFFECT OF SYNTHETIC RESINS DERIVED FROM SYNTOWER BOTTOMS ONTHE PROPERTIES OF TOPPED CRUDES AND ASPHALTS FROM SIMULATED CRUDESCHARGED TO THE REFINERY Composition of Feed Control Additive BlendControl Additive Blend Test No.

Cor. Flash Temp, F Yield, vol 01'430 F+ AP! Gravity at 60 F Penetration,mm/

200 gj sec/39.2 F g/ 5 sec/77 F Penetration Ratio Viscosity SFS. 210 FSFS. 275 F Poises, F

Ductility, cm

1 sin/min, 39.2 F

S cm/min, 77 F Softening Point, R & B, F Spot Test (1 Solubility. CCL,wt 5:

Pos

Pos 99.53

Pos 99.85

Pos 99.97

(1) Positive spot denotes the presence 01' watt. not cracking.

Table 11 Table 1X PREPARATION AND PROPERTIES OF ASPHALTIC RESINSPREPARED FROM SOLVENT GAS OIL FEEDSTOCK D (TABLE ll First Stage SecondStage Air Blowing Catalytic Treatment Run Number K L M N P MaterialCharged D K L K Blend Catalyst used NONE NONE ZnCl, ZnCl, Wt. I:Catalyst NONE NONE 1.0 1.0 Gas used in test air air CH. CH. Gas rate,SCFH 2.0 2.0 1 1 Reaction Temperature, "F. 515 550 560 560 ReactionTime, Hours 5.5 7.0 6.0 6.75 API Gravity at 60 F. 19.4 17.1 19.7 18.1Specific Gravity. 60/60'F. 0.9377 0.9522 0.9358 0.9459

ASTM D 1160 Distillation IBP 'F. 874 901 886 Distillation ResiduePercent of Product 88.8" 87.6 94.4 88.6 Viscosity, SFS, 210' F. 27" 50.581.0 35.9 63 m Estimate.

Blend of 40 wt. I: of Run N and 60 wt. 5 ol'Run M. "Calculated viscosityfrom Run N t! M assuming a straight line function.

Similar tests were made in which synthetic resins prepared from solventgas oil, Table 1X, was used as an additive for the 430 F+ topped whichwas then topped to 650 F and vacuum flashed to yield asphalts. Resultsfollow in Table X:

Table X EFFECT OF SYNTHETIC RESINS DERIVED FROM SOLVENT GAS OIL ON THEPROPERTIES OF TOPPED CRUDES AND ASPHALTS FROM SIMULATED CRUDES CHARGEDTO THE REFINERY Composition of Feed Control Additive Blend Topped Crude.430 F+, wt l00.0 96.0 Product P". wt 0.0 4.0 API Gravity, 60 F 26.l 25.8

Distn. to Yield 650 F+Btms.

Yield. vol of 450 F+ Feed 590 59.9 API Gravity at 60 F 20.3 20.1Specific Gravity, 60/60 F 0.9321 0.9334 Viscosity, SUS at 210 F [12.0l24.l Viscosity, SFS at 122 F 93.2 128.4 Pour Point, F +95 +100 Sulfur.wt 1.60 1.40 Carbon Residue, Rams. 92: 6.73 7.59 Ash. wt 0.02 0.04 Ni,ppm Fe. ppm V, ppm l2.0

Vacuum Asphalt Properties Control Additive Blend Test No. l 2 6 7 8 Cor.Flash Temp, F 960 975 960 970 975 Yield, vol of 430 F+ 36.4 33.6 39.738.8 36.4 API Gravity at 60 F 9.9 9.l l0.4 l0.3 9.8

Penetration, rum/l 200 3/60 sec/39.2 F 25 46 37 3| 100 g/ 5 sec/77 F 13573 l85 146 I03 Penetration Ratio 25.9 34.2 24.9 25.3 3.1

Viscosity SFS. 210 F 442 849 H9 441 653 SH, 275 F 70.7 112.4 58.2 71.196.8 Poises. 140 F 265.3 862.4 171 29l.6 491.1

Ductility. cm I cm/min., 39.2 F 4.5 6.5 ll.5 6.5 5.5 5 cm/min., 77 F 86I08 54 59 83 Softening Point, R&B, F I18 I24 H5 H8 120 Spot Test l PosPos Pos Pos Pos Solubility. CCl wt 99.94 99.83 99.90 99.95 99.90

( 1) Positive spot denotes the presence of wax, not cracking. See Table1x The preceding test data show that synthetic asphaltic Table XI resinsprepared by the two-stage treatment of syntower PREPARATloN AND -r155 0sms PREPARED and solvent as oil were effective as additives for irn-FROM A g MIXTURE OF SYNTOWER BOTTOMS AND SOLVENT GAS OIL proving thequality of paving asphalts derived from crudes being processed at arefinery.

Th d blt' h tht' '1 SW e secon ta u a ion s ows a 511111 at resms pre-Firs 5mg: Camp/tic pared from the solvent gas 011 derlved from the sameAir Blowmg Treatment crudes in the plant were not as effective. Sincesolvent product No. R extraction would have been used to prepare the as-Syntower Solvent phalts in the plant instead of vacuum reduction, whichS 'f: 2 1 LLM 'L Blend Cll l 1C8 IOIl was used Ill the laboratory, moreof the unreacted parcamlys! Used NONE NONE Zncl2 affinlc portions of thesolvent gas oil additive would gngc tal st NQNE NQNE C13 35 so all allhave been extracted ttrom the asphalt, thereby leaving Gas Rm SCFH m w Wmore aromatic resins 1n the asphalt phase. Therefore it ReactionTemperature, "F 375 530 560 is contended, reasonably and as one skilledin the art ig i gg g z g i will understand, that further improvement inthe ductils ifi Gm'my, /60? 019745 ity of asphalts prepared by solventextraction to the 650 50 ASTM D "60 D- F+ feed would have been apparentthan observed for 693 the vacuum asphalts prepared in the laboratory. 2%743 A similar series of tests were made in which a mixture 3:: 3115(7)of air blown and ZnCl, treated syntower bottoms and 20% 853 solvent gasoil was added to the 430 F+ topped crude 55 30% B89 40% 935 which wasthen further distilled and vacuum flashed to yield asphalts. Results arepresented in Tables XI and Dismation Residue X1]. Percent of Product56.0

Table XI-continued PREPARATION AND PROPERTIES OF RESINS PREPARED FROM AMIXTURE OF SYNTOWER BOTTOMS AND SOLVENT GAS OIL Second Stage First StageCatalytic Air Blowing Treatment Viscosity. SFS. 210F 72.2

Blend consisted ol'47.7 wt. A and 52.3 wt. 1' D. "See Table 1 Table XII10 No. Avg. Mol. Wt., ZOO-1,000

Paraffin Hydrocarbon Content, Wt. percent, 01-80 at an elevatedtemperature in the range of from about EFFECT OF SYNTHETIC RESINSDERIVED FROM SYNTOWER BTMS. AND SGO ON THE PROPERTIES OF TOPPED CRUDESAND ASPHALTS FROM SIMULATED CRUDES CHARGED TO THE REFINERY Compositionof Feed Control Additive Blend Topped Crude. 430 F+wt 100.0 960 ProductR, wt.% 0.0 4.0 API Gravity. F 26.1 25.8

Distn. to Yield 650 F+ Btms.

Yield. vol of 450 F+ Feed 59.0 59.1 API Gravity at 60 F 20.3 19.6Specific Gravity. 60/60 F 0.9321 0.9365 Viscosity. SUS at 210 F 112.0118.6 Viscosity. SFS at 122 F 93.2 95.7 Pour Point, F Sulfur, wt. 1.601.45 Carbon Residue. Rams. 7: 6.73 7.03 Ash. wt. 0.02 003 Vacuum AsphaltProperties Control Additive Blend Test No. l 2 9 10 l l Cor. FlashTernp.. F 960 975 960 965 970 Yield, ol 7: of 430 F+ 36.4 33.6 37.8 34.9API Gravity at 60 F 9.9 9.1 10.0 9.5 9.0

Penetration, min/10 200 gso sec/39.2 F 35 25 38 34 27 100 g/ 5 sec/77 F73 160 133 88 Penetration Ratio 25.9 34.2 23.8 25.6 30.7

5 Viscosity SFS. 210 F 442 849 373 470 692 SFS, 275 F 70.7 112.4 62.272.4 97.6 Poises. F 265.3 862.4 187.9 261.0 521.2

Ductility. cm 1 cm/min, 39.2 F 4.5 6.5 10.5 7.0 5.5 5 cm/min, 77 F 86108 76 76 119 Softening Point. R&B, F 118 124 113 116 120 Spot Test 1Pos Pos Pos Pos Pos Solubility. CCl wt. 1: 99.94 99.83 99.96 99.93 99.98

{1) Positive spot denotes the presence of wax. not cracking. Table X1Reasonable modification are possible within the scope of the foregoingdisclosure and the appended claims to the invention the essence of whichis that there are produced by a combination of steps, i.e., air blowingat elevated temperature and then while still at elevated temperaturetreating with a catalyst an oil as herein described to produce apetroleum resin containing material which then, according to theinvention, as such or in at least partly concentrated form is added to atopped crude or asphalt or similar material from which a final asphaltof, say, paving grade can be produced as by vacuum distillation, solventextraction or otherwise as may be desired.

We claim:

1. A process for producing an additive, suitable for use in theproduction of high quality asphalt usable for paving said additivecontaining petroleum resin, which 350 to about 600F for a period of timesufficient at said temperature to produce a treated fraction containingresin-forming materials and (2) subsequently, heating to a temperaturein the range of about 500 to about 55 600F said treated fraction in thepresence of a catalyst chosen from among ZnCl,, FeCl,, and SnCl, toproduce a treated hydrocarbon oil fraction which contains petroleumresin.

2. A process for the preparation of an asphalt suitable 60 for producingpaving grade asphaltic material which 65 to recover an asphaltcontaining said petroleum resin.

3. A process according to claim 1 wherein the petroleum resin-containingmaterials are derived from a first bottoms fraction derived infractionating a synthetic hydrocarbon mixture produced in a catalyticcracking A method according to claim 5 wherein P of virgin gas on uct ofclaim 1 is solvent deoiled to obtain concentrated t si de 4. Anoperation according to claim 2 wherein the peresm and sand concemm ed ren ad d t the as phalt. troleum resin-containing material IS firsttreated to re- 5 7 Operation f l i 2 h i said removing of hymovehydrocarbon oil at least partly thereby concendrocarbon oil is by vacuumdistillation. trating said petroleum resin-containing material and emethod of Cl 2 ere n Said remo ing of hydrocarbon oil is by solventextraction.

then said petroleum resin-containing material is added 9. The method ofclalm 4 wherein said removing of to said base material.

h d f h It h m hydrocarbon Oil is by vacuum distillation. A met 0 omprovmg an asp a w 10. The method of claim 4 wherein said removing ofprises recovering the resin from the product of claim 1 hydrocarben i bysowem extraction, and adding the recovered resin to an asphalt.

1. A PROCESS FOR PRODUCING AN ADDITIVE, SUITABLE FOR USE IN THEPRODUCTION OF HIGH QUALITY ASPHALT USABLE FOR PAVING SAID ADDITIVECONTAINING PETROLEUM RESIN, WHIGH PROCESS COMPRISES (1) AIR BLOWING AHYDROCARBON OIL FRACTION HAVING THE FOLLOWING PROPERTIES: API GRAVITY,60*F, 2.0-30 ANILINE POINT, *F, 75-230 VISCOSITY, SFS, 122*F, 5-500 H/CMOL RATIO, 1.2-2.0 IBP, *F, 500-1000 50 PERCENT POINT, *F, 700-1000CARBON RESIDUE, RAMS., PERCENT, 0.2-18 NO. AVG. MOL. WT., 200-1,000PARAFFIN HYDROCARBON CONTENT, WT. PERCENT, 0.1-80 AT AN ELEVATEDTEMPERATURE IN THE RANGE OF FROM ABOUT 350* TO ABOUT 600*F FOR A PERIODOF TIME SUFFICIENT AT SAID TEMPERATURE TO PRODUCE A TREATED FRACTIONCONTAINING RESIN-FORMING MATERIALS AND (2) SUBSEQUENTLY, HEATING TO ATEMPERATURE IN THE RANGE OF ABOUT 500* TO 600*F SAID TREATED FRACTION INTHE PRESENCE OF A CATALYST CHOSEN FROM AMONG ZNCL2, FECL3, AND SNCL2 TOPRODUCE A TREATED HYDROCARBON OIL FRACTION WHICH CONTAINS PETROLEUMRESIN.
 2. A process for the preparation of an asphalt suitable forproducing paving grade asphaltic material which comprises incorporatinga petroleum resin-containing material of claim 1 into a base materialselected from among an asphalt and topped crude to produce a mixture andremoving hydrocarbon oil from said mixture to recover an asphaltcontaining said petroleum resin.
 3. A process according to claim 1wherein the petroleum resin-containing materials are derived from afirst bottoms fraction derived in fractionating a synthetic hydrocarbonmixture produced in a catalytic cracking of virgin gas oil.
 4. Anoperation according to claim 2 wherein the petroleum resin-containingmaterial is first treated to remove hydrocarbon oil at least partlythereby concentrating said petroleum resin-containing material and thensaid petroleum resin-containing material is added to said base material.5. A method of improving an asphalt which comprises recovering the resinfrom the product of claim 1 and adding the recovered resin to anasphalt.
 6. A method according to claim 5 wherein the product of claim 1is solvent deoiled to obtain concentrated resin and said concentratedresin is added to the asphalt.
 7. Operation of claim 2 wherein saidremoving of hydrocarbon oil is by vacuum distillation.
 8. The method ofclaim 2 wherein said removing of hydrocarbon oil is by solventextraction.
 9. The method of claim 4 wherein said removing ofhydrocarbon oil is by vacuum distillation.
 10. The method of claim 4wherein said removing of hydrocarbon oil is by solvent extraction.